JP2009525584A - Large area organic electronic device and manufacturing method thereof - Google Patents

Abstract

A method of manufacturing an organic electronic device is provided. Specifically, a method for producing an organic electroluminescent device having an active polymer layer is provided. The active polymer layer is placed by a web coating method such as microgravure coating. The active polymer layer is patterned by a solvent wiping method.
[Selection] Figure 5

Description

  The present invention relates to a method for manufacturing a large area organic electronic device.

  A large-area semiconductor organic device (light source) that generates light from electrical energy and a device (photovoltaic device) that generates electrical energy from light can be used in various applications. For example, the development of highly efficient light sources comparable to traditional area light sources such as fluorescent emission continues. Electroluminescent devices such as light emitting diodes have been put into practical use for indicator lighting and numeric displays so far, but as light emitting diode technology advances, the benefits of using such technology for area lighting are increasing. . Light emitting diodes (LEDs) and organic light emitting diodes (OLEDs) are solid state semiconductor devices that convert electrical energy into light. LEDs use inorganic semiconductor layers to convert electrical energy to light, while OLEDs use organic semiconductor layers to convert electrical energy to light. In general, to manufacture an OLED, a large number of organic thin film layers are disposed between two conductors or electrodes. Usually, the electrode layer and the organic layer are disposed between two substrates. Light is generated when a current is passed through the electrodes. Unlike traditional LEDs, OLEDs can be processed using low cost large area thin film deposition methods. OLED technology is suitable for making ultra-thin light emitting displays and for other large area applications. Active developments have been made to achieve general purpose area lighting using OLEDs.

  Photovoltaic (PV) devices can be made using similar materials and concepts as LED devices. Semiconductor PV devices are generally based on the separation of electron-hole pairs formed after absorption of photons from a light source such as sunlight. A normal electric field is applied to facilitate charge separation. The electric field arises from a Schottky contact where a built-in voltage exists at the metal-semiconductor interface or from a pn junction between p-type and n-type semiconductor materials. Such devices are usually made from inorganic semiconductors, particularly silicon, which can be either single crystal, polycrystalline or amorphous structures. Usually, silicon is selected because the photon conversion efficiency is relatively high. However, silicon technology combines high cost with complex manufacturing processes, and the resulting device is expensive compared to the power it generates.

  Like OLEDs, organic photovoltaic (OPV) devices are based on active semiconductor organic materials, but have recently gained more attention as a result of advances in organic semiconductor materials and are increasingly used for large area applications. It has come to be. These materials guarantee good efficiency that could not be achieved with previous OPV devices. Typically, the active component of an OPV device is two or more layers of organic semiconductor material disposed between two conductors or electrodes. At least one organic semiconductor material layer is an electron acceptor and at least one organic material layer is an electron donor. An electron acceptor is a material that can accept electrons from another adjacent material due to its high electron affinity. An electron donor is a material that can accept holes from adjacent materials due to its low ionization potential. When the organic photoconductive material absorbs photons, bound electron / hole pairs are formed, and charge collection cannot occur unless these electron / hole pairs are dissociated. The separated electrons and holes move through the respective acceptors (semiconductor materials) and are collected by the opposite electrode.

  The specific layer of organic semiconductor material incorporated in the PV device may differ from the specific layer of organic material incorporated in the OLED device, but similar design due to the similar structure of the OPV device and the OLED device And there are manufacturing issues. As an example, the techniques used to manufacture OLED devices can also be used to manufacture OPV devices, and vice versa. Therefore, similar problems and issues are recognized when manufacturing large area OLED devices and large area OPV devices.

  One challenge in manufacturing large area organic electronic devices such as OLEDs and OPVs is how to arrange the active polymer layer. For example, an OLED typically includes a light emitting layer, an electron transport layer, and a hole transport layer between two electrodes. The usual method of applying such an organic electroluminescent layer to a large area is expensive due to high processing cost and processing restrictions. A common method of placing the active polymer layer is spin coating, which spreads a liquid film on a rotating substrate at high speed. However, this approach is limited to small area coatings due to spin chamber dimensional constraints. Furthermore, spin coating is a batch operation. In the spin coating method, 99% or more of the coating solution is wasted, resulting in high material costs.

Another design challenge associated with the fabrication of large area organic electronic devices is the patterning of the active polymer layer. In order to meet device design specifications and to increase device yield, organic layers including active polymer layers are often patterned into various textures, topography and geometries. The patterning of the active polymer layer is conventionally performed using laser ablation. In this case, an area to be patterned is covered with a patterning photomask, and the remaining area is selectively etched using a laser beam. One problem associated with active layer patterning in such organic electronic devices is that this process is not compatible with plastic substrates. The laser beam generates significant local heat, which can damage the substrate due to the large mismatch between the electrode material and the thermal expansion coefficient of the underlying plastic substrate. Furthermore, the process is extremely slow and expensive and cannot be easily performed on large samples or in field work.
US Patent Application Publication No. 2005/0129977 US Patent Application Publication No. 2004/0121508 International Publication No. 01/18889 Pamphlet

  Therefore, there is a need for excellent film formation and patterning methods in the manufacture of large area organic electronic devices.

  According to one embodiment of the present invention, a method for manufacturing an organic electronic device is provided. The method includes a step of disposing a first active polymer layer on the first electrode by a web coating method, a step of disposing a second active polymer layer on the first active polymer layer by a web coating method, and a first step by solvent wiping. And patterning at least one of the second active polymer layers.

  According to another embodiment of the present invention, a method for producing a large area array of organic electronic devices is provided. The method includes the steps of disposing a conductive layer on a flexible substrate, patterning the conductive layer to form a plurality of electrically isolated conductive regions, and applying a first active polymer layer to the conductive layer by a web coating method. And a step of disposing the entire conductive layer so as to cover the first active polymer layer. The method further includes patterning the first active polymer layer to form a plurality of separated first active polymer regions, wherein each of the plurality of separated first active polymer regions includes a plurality of separated first active polymer regions. Patterning is performed to cover at least a portion of a corresponding one of the electrically isolated conductive regions, and the patterning is performed by solvent wiping.

  According to another embodiment of the present invention, a method for manufacturing an organic light emitting diode system is provided. The method includes a step of disposing a hole transport layer on a flexible substrate on which a plurality of first electrodes are patterned. At this time, the hole transport layer is disposed by a web coating method. The method further includes patterning the hole transport layer by solvent wiping, placing the light emitting polymer layer on the hole transport layer by web coating, and patterning the light emitting polymer layer by solvent wiping.

  In order that the above and other features, aspects and advantages of the present invention may be better understood, embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the drawings, the same reference numerals denote the same parts.

  First, FIG. 1 shows an array 10 of organic devices 12. Any number of organic devices 12 may be included in the array 10. Furthermore, the array 10 can be configured to be used as a large area array of the organic devices 12 as will be described later. As used herein, the terms “configure”, “arrange” (to be), etc. refer to the dimension or arrangement of an element to form a particular structure, to achieve a particular result, or to an element Is manufactured as such. The organic device 12 may be, for example, an organic photovoltaic device (OPV) or an organic light emitting diode (OLED). As described above, the organic device manufacturing method is the same regardless of the type of device. As is well known, the specific material layers and wirings (interconnections) of the electrodes vary, but similar techniques can be used to deposit and pattern the layers.

  Each organic device 12 of the array 10 can be manufactured on a film or sheet of flexible transparent material. The flexible transparent material can be configured to form a substrate 14 for the array 10. The flexible substrate 14 can be formed from any suitable material, such as polyethylene terephthalate (PET), polycarbonate (eg, Lexan), polymer material (eg, Mylar), polyester, metal foil, and the like. In one embodiment, the substrate 14 is formed from a material having a high melting point, thereby allowing high processing temperatures (eg,> 200 ° C.). Further, the substrate 14 is advantageously transparent and has a high visible light transmittance (eg, transmittance> 85%). Furthermore, the substrate 14 is advantageously formed from a material having, for example, high impact strength, flame retardancy and thermoformability.

  In one embodiment, the substrate 14 may be about 4 feet long and about 1 foot wide, for example. Of course, substrates 14 having other desirable dimensions may be used. The substrate 14 can range from about 1 to 125 mils thick. In general, a material less than 10 mils thick can be expressed as a “film”, while a material greater than 10 mils thick can be expressed as a “sheet”. The substrate 14 may be a film or a sheet. Further, although these terms imply specific thicknesses, they are used here as interchangeable terms. Therefore, any terminology is not intended to limit the thickness of each material and is sometimes used for convenience. In general, the thinner substrate 14 is a lighter and less expensive material. However, a thicker substrate 14 provides higher rigidity and thus provides structural support suitable for large area organic devices. Thus, the thickness of the substrate 14 depends on the particular application.

  According to a particular embodiment of the invention, it is advantageous that the substrate 14 is flexible and can be fed out of, for example, a roll. Further, by using a roll for the substrate 14, a large capacity of the active portion, low cost, and reel-to-reel processing and manufacturing can be performed. The roll can be, for example, 1 foot wide. The substrate 14 may be cut to a length suitable for a particular application.

  As will be apparent to those skilled in the art, for large area applications, the organic electronic devices 12 are arranged to form a pattern or array. That is, the array is patterned or “pixeled” to form individual electrically isolated patches or dense layers of “pixels”. By pixelating one or more layers of each individual device 12, a short circuit between the upper and lower electrodes only affects the shorted pixels, not the entire array. Such methods are known to mitigate complete damage to organic electronic devices and are described in detail below.

  Referring now to FIG. 2, a simplified cross-sectional view of the organic electronic device 12 taken along section line 2-2 of FIG. 1 is shown. The organic electronic device 12 of FIG. 2 is a single pixel display of the array 10, for example. In this embodiment, the organic electronic device constitutes an OLED. As described above, the organic electronic device (OLED) 12 includes a substrate 14, a first electrode 16, active polymer layers 18 and 20, and a second electrode 22. The first electrode 16 is configured to form the anode of the OLED and can contain a transparent conductive oxide (TCO), such as indium tin oxide (ITO). Transparent ITO can be placed on the flexible transparent substrate 14 using a roll-to-roll processing method. For example, the 1st electrode 16 can be arrange | positioned by sputtering method, and can be formed in the thickness of the range of about 50-250 nm. The light transmission ratio of the first electrode 16 is preferably 0.8 or more.

  The second electrode 22 is configured to form a cathode. The second electrode 22 can be formed from, for example, an aluminum film to which a cathode activator NaF is added. Alternatively, the second electrode 22 can contain, for example, calcium, magnesium, or silver. Similar to the first electrode 16, the second electrode 22 can also be disposed by a sputtering method and can be deposited to a thickness in the range of about 50 to 250 nm, for example. In the case of a bottom extraction OLED device, it is advantageous that the second electrode 22 is reflective and reflects impinging light towards the front of the device (which extracts the light to the surrounding environment). As is well known, light is emitted from the active polymer layers 18 and 20 when a voltage potential is applied between the first electrode 16 and the second electrode 22. Alternatively, a transparent light emitting device can be realized by making both electrodes transparent, or in the case of a top take-out OLED, the bottom electrode can be made reflective and the top electrode can be made transparent.

  As described above, multiple active polymer layers can be disposed between the first electrode 16 and the second electrode 22. In the case of OLED devices, the active polymer layer typically comprises a number of layers of organic light emitting polymers such as polyphenylene vinylene, polyfluorene, etc. from a xylene solution. As will be apparent to those skilled in the art, the number of layers and the type of organic polymer will vary depending on the application. In one embodiment of the OLED device, the active polymer layer 20 contains a light emitting polymer (LEP) such as polyfluorene, and the active polymer layer 18 is poly (3,4) -ethylenedioxythiophene / polystyrene sulfonate (PEDOT). Hole transport layer such as / PSS). Other light emitting polymers and hole transport or electron transport layers may be used. In addition, additional active polymer layers can be used in OLED devices.

  If the organic electronic device 12 is an OPV device, the type of organic material used for the active polymer layers 18 and 20 can be different from that described above for the OLED device. The OPV device includes one or more layers that enhance the transport of charge to the electrode, as described above. For example, in an OPV device, the active polymer layers 18 and 20 can include an electron donor material and an electron acceptor material. The electron donor layer is, for example, a metal-free phthalocyanine; copper, zinc, nickel, platinum, magnesium, lead, iron, aluminum, indium, titanium, scandium, yttrium, cerium, praseodymium, lanthanum, neodymium, samarium, europium, Phthalocyanine dyes containing gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; quinacridone dyes; indigo and thioindigo dyes; merocyanine compounds; cyanine compounds; squalium compounds; hydrazone; Conjugated conductive polymers such as polypyrrole, polyaniline, polythiophene, polyphenylene, poly (phenylene vinylene), poly (thie Vinylene), poly (iso thianaphthalene); and can contain poly (silane). Further, electron donor materials include hole transport materials such as triaryldiamine, tetraphenyldiamine, aromatic tertiary amine, hydrazone derivative, carbazole derivative, triazole derivative, imidazole derivative, oxadiazole derivative having amino group And polythiophene.

Electron acceptor materials in OPV devices include, for example, perylenetetracarboxydiimide, perylenetetracarboxydiimidazole, anthraquinone acridone dye, polycyclic quinone, naphthalenetetracarboxydiimidazole, CN and CF ₃ substituted poly (phenylene vinylene) and back Minster fullerene is mentioned. In addition, electron acceptor materials include electron transport materials such as metal organic complexes of 8-hydroxyquinoline; stilbene derivatives; anthracene derivatives; perylene derivatives; metal thioxinoid compounds; oxadiazole derivatives and metal chelates; pyridine derivatives; Also included are quinoline derivatives; quinoxaline derivatives; diphenylquinone derivatives; nitro-substituted florin derivatives; and triazines.

  As described above, the flexible substrate 14 is advantageous because it is compatible with reel-to-reel processing. Therefore, the deposition and patterning of the active polymer layers 18 and 20 are more difficult than for example for ordinary small area indicator lighting OLEDs and small OPV devices. A number of coating steps are performed to deposit the various layers that make up the active polymer layers 18 and 20 and to pattern these layers. Accordingly, the description of the deposition and patterning of the active polymer layers 18 and 20 typically refers to a number of repeated coating steps, which are described in connection with FIG. 5 and specifically in the examples. It is. According to an embodiment of the present invention, each of the active polymer layers 18 and 20 is disposed by a web coating method, such as the Yasui Seiki microgravure method. According to another embodiment of the invention, each of the active polymer layers 18 and 20 is patterned using a solvent wiping (SAW) method. The film formation and patterning method will be described with reference to FIGS.

  According to an embodiment of the present invention, the active polymer layers 18 and 20 are deposited by any suitable web coating method. The web coating method is generally advantageous because less material is wasted than other film forming methods. The web coating method can be used with a roll-to-roll manufacturing system. Furthermore, the web coating method can be easily used for the manufacture of large area devices such as large area OLEDs and OPVs.

  One example of a web coating method for placing the active polymer layers 18 and 20 is Microgravure Coating® using a system available from Yasui Seiki. Microgravure coating is a special continuous coating process that is configured to apply a thin, uniform layer of a low viscosity liquid. An example of a micro gravure coating system is shown by 24 in FIG. A small-diameter engraving roll (gravure roll) 26 engraved with patterns, cells or grooves is prepared. On the surface of the gravure roll 26, a large number of cells that determine the internal capacity of a finite volume are provided at regular intervals. By varying the cell geometry, number, spacing, depth and other parameters, a range of total volume can be generated to achieve coating volume (thickness) control. The micro gravure roll is mounted on a bearing and rotates in a partially immersed state in the coating liquid pan 28. The coating liquid pan 28 is filled with a liquid 30 to be applied to the web 32. According to embodiments of the present invention, the liquid 30 can contain an active polymer material, such as a LEP or PEDOT layer, and the web 32 can be a flexible substrate material. More specifically, the web 32 can be a flexible substrate 14 coated with ITO that forms the first electrode 16. The liquid 30 can contain a material that is disposed on the ITO coated flexible substrate 14 to form the first active polymer layer 18 (which can be, for example, a PEDOT layer). A similar process can be used to place the second active polymer layer 20 (which can be, for example, a LEP layer) over the first active polymer layer 18.

  During production, the gravure roll 26 is immersed in the liquid 30 while the web 32 is guided over the gravure roll 26 by rolls 34 and 36. The rollers 34 and 36 are configured to guide the roll 30 to the gravure roll 26 in an upward contact relationship. When the web 32 reaches the gravure roll 26 covered with the liquid 30, the cells or grooves on the surface of the gravure roll 26 are filled. As the gravure roll 26 rotates, the liquid 30 is scraped and as the gravure roll 26 rotates toward the point of contact with the web 32, the liquid 30 is scraped (pre-weighed) by the flexible steel blade 38. The excess liquid is scraped off from the surface of the gravure roll 26 by the blade 38. The gravure roll 26 is reversely wiped against the moving reel-to-reel surface (for example, the substrate 14 on which the ITO layer 16 is formed), and a part of the liquid accumulated on the engraving surface of the gravure roll 26 is removed. Transfer to the surface. Since microgravure coating is a continuous coating method, the disposed layers can then be patterned as described below.

  According to embodiments of the present invention, other web coating methods may be used to place the active polymer layers 18 and 20. For example, each of the active polymer layers 18 and 20 can be disposed using forward or reverse roll coating, direct forward gravure coating, offset gravure, flexographic printing, screen printing, ink jet printing. Flexographic printing is a method in which an area to be printed is a protrusion on a flexible plate attached to a roll. After the coating is transferred from the engraving roll to the convex image, the coating is transferred to the surface. Rotary screen printing uses a squeezer to extrude the coating through the open area of the fine fabric mesh to the substrate. In inkjet printing, first, droplets are formed on the nozzles of an inkjet device. A droplet is sent out on the surface, and when the droplet hits the surface, the droplet is spread by inertia force and surface tension.

  After the active polymer layer 18 or 20 is placed, the layer can be patterned to form an isolation structure or pixel of the array 10 as shown in FIG. According to embodiments of the present invention, solvent wiping (SAW) methods can be performed to pattern the active polymer layers 18 and 20. The SAW method uses a portion of material, such as active polymer layer 18 and one or more solvents of water, methanol, ethanol, isopropanol, acetone, toluene, xylene, or combinations thereof, to achieve material removal in selected areas. A portion of 20 is solvated. The surface of the solvated portion of the active polymer layer 18 or 20 is then wiped with a wiping head to remove a portion of the active polymer layer 18 and / or 20, thus patterning these layers. As described below, in one embodiment of the present invention, after the active polymer layer 18 is disposed and patterned, the active polymer layer 20 is disposed and patterned. Alternatively, active polymer layers 18 and 20 can be placed and then patterned simultaneously. Wiping head is usually sponge, elastomer, thermoplastic resin, thermosetting resin, fiber mat, porous material, polyurethane rubber, synthetic rubber, natural rubber, silicone, polydimethylsiloxane (PDMS), surface textured material and combinations thereof 1 or more types of. Further, the wiping head can have a desired profile (shape) that achieves the desired patterning of the underlying layer.

  In an embodiment of the present invention, the solvating species is selected to remove one active polymer layer 18 or 20 in a single wiping operation without damaging the underlying layer. In this embodiment, the active polymer layer 18 can be disposed and then patterned. The active polymer layer 20 can then be placed and then patterned. The solvent used for patterning of each layer differs depending on the material of the layer to be patterned. For example, the LEP layer in a two-layer structure can be patterned using xylene as a solvent without damaging the underlying PEDOT layer.

  In another embodiment, the solvating species is selected such that multiple active polymer layers 18 and 20 can be removed in a single wiping operation. That is, both active polymer layers 18 and 20 can be placed and then both active polymer layers 18 and 20 can be patterned simultaneously. In a typical example, the active polymer layer 18 is a conductive polymer film, such as PEDOT, that is highly polar and dissolves only in a hydrogen bonding solvent such as water. The active polymer layer 20 is nonpolar and can contain a LEP material that is soluble only in a nonpolar solvent such as toluene or xylene. In order to remove a plurality of polymer films having such extremely different solubility characteristics by one wiping operation, a solvent suitable for each polymer is dispersed in a third solvent to form a homogeneous solution. The third dispersing solvent can be a number of solvents such as alcohols (eg, isopropanol, ethanol, methanol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), acetates, ethers, methylene chloride, or intermediate solubility parameters. Is selected from any solvent having In this embodiment, the two active polymer layers 18 and 20 can also be removed in one step with a solvent system containing water and xylene. In this particular embodiment, isopropanol is used to facilitate the mixing of water and xylene to produce a homogeneous solution.

  As described above, various layers are placed and patterned to ensure proper electrical paths to form an array 10 (FIG. 1) of organic electronic devices 12. In one embodiment, adjacent devices 12 in a single row are connected in series to obtain a short-circuit resistant design structure. FIG. 4 shows a design example of three organic electronic devices 12 electrically connected in series. 4 is a cross-sectional view of the three devices 12 taken along section line 4-4 of FIG. Of course, the embodiment shown in FIG. 4 is merely exemplary. Other arrangements can also be used.

  Specifically, FIG. 4 shows three organic electronic devices 12 coupled in series. The first electrode 16 can be disposed and patterned to form the separation structure shown in FIG. As described above and as will be described later, each of the overlying layers such as the active polymer layers 18 and 20 and the second electrode 22 can be disposed and patterned as shown. In the embodiment of FIG. 4, each second electrode 22 is positioned and patterned to ensure a conductive path to the first electrode 16 of an adjacent device in a single row of the array. By connecting each of adjacent devices in a single row in series, a structure that is resistant to electrical short-circuiting (short-circuit-proof structure) can be obtained.

  According to embodiments of the present invention, by employing a web coating method to place the active polymer layers 18 and 20, and employing a solvent wiping method (SAW) to pattern the active polymer layers 18 and 20, Simplifies the manufacture of organic electronic devices. Strictly speaking, the process of manufacturing an organic electronic device according to an embodiment of the present invention varies depending on the particular device to be manufactured, the desired structure of the array, and the type of material to be deposited. However, such variations of the methods disclosed herein are within the expectation of those skilled in the art. Also, a number of baking and processing steps can be used. Baking and processing steps will vary depending on the material being deposited, the thickness of the material, the type of underlying material, and other design variables that can be anticipated by one skilled in the art.

  Referring now to FIG. 5, a simplified process 40 for manufacturing an array of organic electronic devices according to an embodiment of the present invention is depicted in a flowchart. First, as shown in block 42, a first electrode is formed. The first electrode may be formed by arranging an ITO layer on a flexible substrate and patterning to form a number of separated ITO patterns. Next, as shown in block 44, a first active polymer layer is disposed on the ITO layer. The first active polymer layer is disposed using a web coating method such as microgravure coating (registered trademark). The first active polymer layer can be, for example, a PEDOT layer. Next, as shown in block 46, the PEDOT layer is patterned by a solvent wiping method (SAW). For example, the PEDOT layer may be patterned as shown in FIG. Depending on the particular device to be manufactured, the active polymer layer deposition and patterning can be repeated. In one embodiment, the LEP layer is placed on the PEDOT layer using a web coating method such as Microgravure Coating®. Next, the LEP layer can be patterned by the SAW method to form the structure shown in FIG. Alternatively, after each of the PEDOT layer and the LEP layer is placed, the respective layers may be patterned (block 44). After placing both layers, both layers may be patterned simultaneously by the SAW method (block 46). Finally, as shown in block 48, a second electrode can be placed and patterned. The second electrode can be made of aluminum, for example.

  A person skilled in the art should be able to fully utilize the present invention according to the description of the present specification without further explanation. The following are examples of manufacturing processes and further guidance for those skilled in the art to practice the present invention. The examples are only representative examples of experiments that contribute to the practice of the present invention. Accordingly, these examples do not in any way limit the invention defined in the claims.

  In the examples described herein, a roll of flexible ITO coated PET (4 inch wide web) having a nominal sheet resistance of about 40 ohms / square was prepared. First, a small piece (4 × 6 μm) of ITO-coated PET was cut out and preliminarily cleaned. Prior to coating, the pieces were treated with UV / ozone for 10 minutes to improve surface wettability. The web coating method employed in this example is the microgravure coating method (registered trademark) as described above. That is, after cleaning, clean ITO-coated PET was stitched on the web with a microgravure coating apparatus. When the substrate pretreatment module is merged with the production line, cutting and stitching can be simplified. That is, the ITO-coated flexible substrate itself can be used as a web, and can be directly supplied to the microgravure coating apparatus.

  Next, a hole transport layer (0.75% PEDOT solution, manufactured by Baytron) was applied to the ITO substrate by microgravure coating. The PEDOT solution had a solids concentration of 0.75% by weight and contained approximately 20% isopropanol. The solution was pre-filtered through a 0.45 μm filter and degassed for 5 minutes under reduced pressure. Next, the solution was transferred to a coating liquid pan of a micro gravure coating apparatus. The gravure roll included a triple helix sculpture and was rotated in the opposite direction to the web movement. As a result, a film such as PEDOT can be applied to the ITO / PET substrate by shearing force. Of course, several factors affect film thickness and uniformity. For example, web to gravure roll speed ratio, coating solution concentration, triple helix engraving cell volume, web tension, doctor blade pressure, and web-engraving roll distance all affect film thickness and uniformity. In this example, a 0.75% PEDOT solution was used and the web was fed at about 1-2 m / min, maintaining a speed ratio between the engraving roll and the web in the range of about 1 to about 1.5. After the PEDOT film was deposited on the ITO coated web, the coated PEDOT film was dried in a drying chamber at about 30 ° C. Of course, the temperature can be increased to accelerate the drying process. The stitch ITO coated with PEDOT was then removed from the web and baked off-line in a 110 ° C. oven for 10 minutes. The final thickness of the dried PEDOT film was about 80 nm and the thickness variation was less than 10 nm.

  After baking, the baked PEDOT coated film was stitched again on the web. Both the gravure roll and the liquid container were cleaned and replaced with a light emitting polymer solution. In this example, polyfluorene ADS329BE (manufactured by American Dye Source) was used. The same coating method described above for the PEDOT film was repeated for the formation of the light emitting polymer film. A 1% LEP solution was applied at a web speed of 1 m / min to obtain a uniform film about 100 nm thick. There were no visible defects or thickness variations.

  After depositing uniform PEDOT and LEP layers, the coated sample is then transferred to a solvent wiping (SAW) module where the coating is selectively solvated with a compliant head having a fine textured surface. Removed. In this example, the device was patterned according to the short-circuit resistant design described with reference to FIG. In this example, as described above, both the PEDOT layer and the LEP layer were placed and then these layers were patterned together. Alternatively, each layer can be patterned after deposition of that layer and before deposition of the next layer. Once the PEDOT and LEP layers were patterned, the device was then removed from the web and baked at 110 ° C. for 10 minutes. Next, the second electrode was formed using a normal cathode film formation / sealing method.

  As described above, a method of manufacturing a large area organic electronic device is provided. It is advantageous to arrange the active polymer layers, such as the PEDOT layer and the LEP layer, using a web coating method, such as a microgravure coating method, which realizes production by roll-to-roll processing. Furthermore, the active polymer layer can be patterned by a solvent wiping method. The web coating provides an active polymer layer with a thickness in the range of about 0.01 μm to 1 μm with a thickness variation of less than about 10%. The SAW method achieves a solvent wiping pattern having a geometry in the range of about 10 μm to about 10,000 μm.

  While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and have been described in detail herein. However, the present invention is not limited to a specific form. The present invention includes all modifications, equivalents, and alternatives as falling within the scope of the invention as defined in the claims.

It is a top view which shows the array of the organic electronic device which can be manufactured according to embodiment of this invention. FIG. 2 is a cross-sectional view of the organic electronic device of FIG. 1 that can be manufactured in accordance with an embodiment of the present invention. FIG. 3 is a schematic diagram illustrating a system for placing an active polymer layer of the organic electronic device of FIGS. 1 and 2 in accordance with an embodiment of the present invention. 2 is a cross-sectional view of the multiple organic electronic devices of FIG. 1 that can be manufactured according to embodiments of the present invention. FIG. 2 is a flowchart of a process for manufacturing an organic electronic device according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Array 12 Organic electronic device 14 Board | substrate 16 1st electrode 18, 20 Active polymer layer 22 2nd electrode 24 Micro gravure coating system 26 Gravure roll 28 Coating liquid 30 Coating liquid 32 Web 34, 36 Roll 38 Doctor blade

Claims (28)

A first active polymer layer is disposed on the first electrode by a web coating method;
Disposing the second active polymer layer on the first active polymer layer by a web coating method;
A method of manufacturing an organic electronic device, comprising patterning at least one of the first and second active polymer layers by solvent wiping. The method of manufacturing an organic electronic device according to claim 1, wherein in the step of disposing the first active polymer layer on the first electrode, the first active polymer layer is disposed on a flexible substrate covered with indium tin oxide. The method for producing an organic electronic device according to claim 1, wherein the first active polymer layer is arranged by a microgravure (registered trademark) coating method in the step of arranging the first active polymer layer on the first electrode. The manufacturing method of the organic electronic device of Claim 1 which arrange | positions a positive hole transport layer on a 1st electrode at the process of arrange | positioning a 1st active polymer layer on a 1st electrode. The manufacturing method of the organic electronic device of Claim 1 which arrange | positions a PEDOT layer on a 1st electrode at the process of arrange | positioning a 1st active polymer layer on a 1st electrode. The method for producing an organic electronic device according to claim 1, wherein the light emitting polymer layer is arranged in the step of arranging the second active polymer layer. The method for producing an organic electronic device according to claim 1, wherein in the step of arranging the first active polymer layer, a first active polymer layer having a thickness of about 0.01 μm to 1.0 μm is arranged. The method for producing an organic electronic device according to claim 1, wherein in the step of arranging the second active polymer layer, a second active polymer layer having a thickness of about 0.01 μm to 1.0 μm is arranged. The method of manufacturing an organic electronic device according to claim 1, wherein in the patterning step, the first active polymer layer is patterned before the second active polymer layer is disposed. The manufacturing method of the organic electronic device of Claim 1 which patterns a 1st active polymer layer and a 2nd active polymer layer simultaneously at a patterning process. Placing a conductive layer on a flexible substrate;
Patterning the conductive layer to form a plurality of electrically isolated conductive regions;
The first active polymer layer is disposed on the conductive layer by the web coating method so that the entire conductive layer is covered with the first active polymer layer,
The first active polymer layer is patterned to form a plurality of separated first active polymer regions, each of the plurality of separated first active polymer regions being a plurality of electrically isolated conductive regions. Patterning over at least a portion of the corresponding one and patterning by solvent wiping;
The manufacturing method of the large area array of an organic electronic device including a process. The manufacturing method of the large area array of the organic electronic device of Claim 11 which arrange | positions a conductive layer on a part of roll-shaped flexible material at the process of arrange | positioning a conductive layer on a flexible substrate. The large-area array of organic electronic devices according to claim 11, wherein the first active polymer layer is disposed by a micro gravure (registered trademark) coating method in the step of disposing the first active polymer layer on the conductive layer by a web coating method. Manufacturing method. The method for producing a large-area array of organic electronic devices according to claim 11, wherein the hole transport layer is disposed in the step of disposing the first active polymer layer. The method for producing a large-area array of organic electronic devices according to claim 11, wherein the PEDOT layer is arranged in the step of arranging the first active polymer layer. Further, the second active polymer layer is disposed on the first active polymer layer by the web coating method so as to cover the entire first active polymer layer with the second active polymer layer,
The second active polymer layer is patterned to form a plurality of separated second active polymer regions, wherein each of the plurality of separated second active polymer regions is a plurality of separated first active polymer regions. The method for producing a large-area array of organic electronic devices according to claim 11, comprising the steps of patterning so as to cover at least a part of the corresponding one, and performing patterning by solvent wiping. The method for producing a large-area array of an organic electronic device according to claim 16, wherein the second active polymer layer is arranged by a micro gravure (registered trademark) coating method in the step of arranging the second active polymer layer. The method for producing a large-area array of organic electronic devices according to claim 16, wherein the light-emitting polymer layer is disposed in the step of disposing the second active polymer layer. Furthermore, the manufacturing method of the large area array of the organic electronic device of Claim 16 including the process of arrange | positioning a 2nd conductive layer on a 2nd active polymer layer. The method for producing a large area array of organic electronic devices according to claim 16, wherein the step of patterning the first active polymer layer and the step of patterning the second active polymer layer are performed simultaneously. A hole transport layer is disposed on a flexible substrate on which a plurality of first electrodes are patterned by a web coating method,
Pattern the hole transport layer by solvent wiping,
The light emitting polymer layer is disposed on the hole transport layer by a web coating method,
Patterning the light-emitting polymer layer by solvent wiping;
A method of manufacturing an organic light-emitting diode system, including a process. The method of manufacturing an organic light emitting diode system according to claim 21, wherein the PEDOT layer is disposed in the step of disposing the hole transport layer. The method of manufacturing an organic light emitting diode system according to claim 21, wherein in the step of arranging the hole transport layer, the hole transport layer is arranged so that the thickness variation is less than 10%. The method of manufacturing an organic light emitting diode system according to claim 21, wherein a layer having a thickness of about 0.01 µm to 1.0 µm is arranged in the step of arranging the hole transport layer. The method of manufacturing an organic light emitting diode system according to claim 21, wherein the hole transport layer is disposed by a micro gravure (registered trademark) coating method in the step of disposing the hole transport layer. The method of manufacturing an organic light emitting diode system according to claim 21, wherein in the step of disposing the light emitting layer, the hole transport layer is disposed such that the thickness variation is less than 10%. The method of manufacturing an organic light emitting diode system according to claim 21, wherein a layer having a thickness of about 0.01 µm to 1.0 µm is arranged in the step of arranging the light emitting layer. The method of manufacturing an organic light emitting diode system according to claim 21, wherein the step of patterning the hole transport layer and the step of patterning the light emitting polymer layer are performed simultaneously.

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